Polymerization process

ABSTRACT

A process for forming polymer material having terminal hydroxyl groups and a number average molecular weight in the range of 500 to 10,000, by (A) forming a single phase polymerization system consisting essentially of hydrogen peroxide, specified vinylidene monomer and/or conjugated diene monomer, and liquid organic mutual solvent diluent comprising at least a major proportion of lower aliphatic saturated oxygenated solvent selected from the alcohols, ether alcohols, keto alcohols and ketones, which system is essentially free of materials that decompose hydrogen peroxide to form oxygen at below 100* C., and (B) heating said system to temperatures sufficiently above 100* C. to initiate and effect polymerization in said system.

United States Patent I Burke, Jr. et al.

[ June 27, 1972 POLYMERIZATION PROCESS Inventors: Oliver W. Burke, Jr.,506 lntracoastal Driye FortLauderda le, Fla. 33304; Joseph Austin A.Kizer, 211 SE. Sixth'GiFt, Pompano Beach, Fla. 33060; Pauls Davis, 30027White St., Gibralter, Mich. 48173 Filed: Jan. 22, 1970 Appl. No.: 4,812

Related US. Application Data US. Cl. ..260/94.2 R, 260/32.8 A;32.8SB;33.4 PQ;82.1;83.5;83.7;85.3 R;85.5 XA;85.5 l-lC;85.5 ES;85.5 B;85.5

260/47 UA, 260/63 BB, 260/67 UA, 260/67.6 R, 260/67.6 C, 260/78.5 B,260/ M, 260/82.1, 260/83.5, 260/83.7, 260/85.3 R, 260/85.5 P, 260/85.7,260/86.l R, 260/86.7, 260/87.5,

260/87.7, 260/88.l R, 260/88.2 E, 2601883 L, 260/88.5, 260/88.7 G,260/89.l 260/89.3, 260/89.5 R, 260/9l.l R, 260/9l.7, 260/92.8 R,260/93.1, 260/93.5 R, 260/635 R, 260/ R [51] Int. Cl ..C08f l/60,C08f3/00, C08f 15/00 [58] Field of Search ..260/32.8 A, 32.8 SB, 33.4PQ, 260/82.l, 83.5, 83.7, 85.3 R, 85.5 XA, 85.5 HC, 85.5 ES, 85.5 B,85.5 P, 85.7, 87.5 C, 87.5 E, 87.5 G, 86.1 R, 86.l E, 86.7, 88.1 R, 88.1P, 88.1PN, 88.1 PA, 88.1 PE, 88.2 E, 88.2 B, 88.2 C; 260/87.7, 88.7 G,89.1, 89.3, 91.1 R, 91.7, 88.3 L, 88.5, 92.8 R, 93.1, 93.5 R, 93.5 S,94.2 R, 95 R, 635 H, 635 E, 78.5 B, 78.5 E, 89.5 R, 89.5 H, 89.5 A,

[5 6] References Cited UNITED STATES PATENTS 1,586,803 6/1926 Hermann etal. .260/87 1,933,052 10/1933 Fikentscher et al. ..260/2 2,377,7526/1945 Britton et al 260/92.8 2,564,292 8/ 1951 Wolf 260/93 5 2,613,22310/1952 Young .....260/635 2,757,210 7/1956 Jenner ..260/635 2,828,1314/1958 Greenspan et al 260/94.2 2,850,540 9/1958 Frank et al 260/6353,049,528 8/1962 Diem ..260/94.2

OTHER PUBLlCATlONS Synthetic Rubber, Whitby et al., John Wiley & Sons1954) Emulsion Polymerization, Bovey et al., Interscience (1955) PrimaryExaminer.loseph L. Schofer Assistant Examiner-John Kight, lllAttorney-Hall & Houghton [57] ABSTRACT A process for forming polymermaterial having terminal hydroxyl groups and a number average molecularweight in the range of 500 to 10,000, by (A) forming a single phasepolymerization system consisting essentially of hydrogen peroxide,specified vinylidene monomer and/or conjugated diene monomer, and liquidorganic mutual solvent diluent comprising at least a major proportion oflower aliphatic saturated oxygenated solvent selected from the alcohols,ether alcohols keto alcohols and ketones, which system is essentiallyfree of materials that decompose hydrogen peroxide to form oxygen atbelow C., and (B) heating said system to temperatures sufficiently above100 C. to initiate and effect polymerization in said system.

20 Claims, 10 Drawing Figures 04 0 name/v5? HAM-7454M) .47" J 51:. fmaa. M M96. now/did United States Patent [151 3,673,168

Burke, Jr. et al. June 27, 1972 a 0/1 w/ as a? POLYMERIZATION PROCESSCROSS-REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of our applications Ser. No. 447,241, filed Apr.12, 1965, and Ser. No. 805,080, filed Jan. 29, 1969; said applicationSer. No. 805,080 having been a continuation of application Ser. No.686,350, filed Nov. 28, 1967; the latter having been a continuation ofapplication Ser. No. 447,196 filed concurrently with said applicationSer. No. 447,241 on Apr; 12, 1965; and said concurrently filedapplications having been continuations in part of our application Ser.No. 863,218, filed Dec. 31, 1959. The foregoing applications wereabandoned in favor of the present application and application Ser. No.101,111 (a further continuation of Ser. No. 447,241), and saidapplication Ser. No. 101,] l 1 is being abandoned in favor of thepresent application.

7 INTRODUCTION AND GENERAL OBJECTS The invention herein disclosedrelates to the production of low molecular weight polymers which haveterminal hydroxyl groups, and aims generally to provide improvedprocesses for such purpose.

A first object of the invention is to provide processes for producingsuch low molecular weight polymers with terminal hydroxyl groups fromethylenically unsaturated monomers.

A second object of the invention is to provide processes for producingsuch low molecular weight polymers with terminal hydroxyl groups fromvinylidene monomers.

Other objects of the invention are to provide processes for producingsuch low molecular weight polymers with terminal hydroxyl groups fromconjugated diene monomers with or without vinylidene monomers.

Other objects of the invention are to provide processes for producingpolymers of these classes which have number average molecular weights inthe range of from 500 to 10,000, and are substantially free of polymericmaterials of higher molecular weight range.

Other objects are to provide processes for producing certain polymers ofthese classes which are water white and essentially free of cloudiness,color or haze.

Other objects are to provide processes for producing polymers of theseclasses which are essentially free of obnoxious odors.

Other objects are to provide processes for producing polymers of theseclasses which contain controlled oxygen content and hydroxylfunctionality.

Still other objects are to provide processes for producing I Suchpolymers in a single phase polymerization employing hydrogen peroxide aspolymerization catalyst under special conditions which contribute to theattaining of the foregoing objects.

Other and further objects and advantages of the invention will becomeapparent from the following description and examples of preferredembodiments thereof.

The invention resides in the novel features and combinations of theprocesses herein disclosed and is more particularly defined in theappended claims.

For ease of reference the present description is indexed by sub-headsand catch-lines which, however, are not to be regarded as limiting theinvention in any way.

SPECIAL AIMS AND UTILITIES In particular embodiments, the inventionresides in a method for forming a polymer material having terminalhydroxyl groups and a number average molecular weight in the range of500 to 10,000, which method comprises:

A. forming a single phase polymerization system of a combination of l.monomer material consisting essentially of one or more polymerizableethylenically unsaturated monomers, preferably having not more than 14carbon atoms, at least one of which has one or more substituents otherthan hydrogen, said monomer material consisting essentially of from 2 topercent by weight of material having a water solubility at 20 C. of nomore than 3.5 weight percent and from 0 to 98 percent byweight ofmaterial having a water solubility at 20 C. greater than 3.5 weightpercent, said ethylenically unsaturated monomer materials excludingdrying oil substances and excluding other non-conjugated polyenecompounds,

2. between 05-10 parts by weight of hydrogen peroxide per 100 parts ofmonomer, and

3. a liquid organic mutual solvent-diluent for all the monomer materialpresent and said hydrogen peroxide and any water present, said liquidorganic mutual solvent-diluent comprising at least a major proportion oflower aliphatic saturated oxygenated solvent selected from the classconsisting of the alcohols, ether-alcohols, keto-alcohols and ketones,preferably the water soluble alcohols,

said system being essentially free of oxygen and of components thatdecompose hydrogen peroxide to form oxygen at less than 100 C., and

B. heating said system at sufficient temperatures in the range of fromabove 100 C. to about 200 C. for a sufficient time to initiate andeffect polymerization.

In one of the preferred embodiments of the just described method themonomer material of clause (A)(l) consists essentially of one or morepolymerizable vinylidene monomers having at least one substituent otherthan hydrogen, said monomer material consisting essentially of from 2 to100 percent by weight of material having a water solubility at 20 C. ofno more than 3.5 weight percent and from 0 to 98 percent by weight ofmaterial having a water solubility at 20 C. greater than 3.5 weightpercent.

In a further preferred embodiment of the above described method themonomer material of clause (A)( 1) consists es sentially of monomermaterial comprising by weight 2-l00 percent conjugated diene monomermaterial and 0 to 98 percent vinylidene monomer material, said monomermaterial consisting essentially of from 2 to 100 percent by weight ofmaterial having a water solubility at 20 C. of no more than 3 .5 weightpercent and from 0 to 98 percent by weight of material having a watersolubility of 20 C. greater than 3.5 weight percent.

By this process the invention 1 achieves polymerization to produce thedesired polymers at adequate and controllable rates of polymerizationwhile avoiding the disadvantages of organic peroxide and organichydroperoxide catalyzed mass polymerizations, e.g. the presence of suchorganic catalyst residues in the product, and also the disadvantages ofemulsion polymerizations, e.g. the presence of emulsifier in theproduct. It also (2) achieves the production of homopolymers andinterpolymers of controlled number average molecular weights in therange of 500 to 10,000, preferably 1,000 to 3,000, from polymerizablemonomer materials as aforesaid. In certain embodiments it also (3)achieves the production of homopolymers or interpolymers of conjugateddiene monomers, or interpolymers of conjugated diene monomers andvinylidene monomers, the diene derived units of which are predominantlyof 1,4-configuration, with the 1,4-configuration itself predominately oftrans 1,4-configtiration, with only a lesser proportion of1,2-configuration. It also (4) provides polymers characterized by thefact that their groups, except for the polymerized monomer materialtherein, are essentially derived from the mutualsolvent-diluent-hydrogen peroxide catalyst systems, e.g. from the C to Calkanolic hydrogen peroxide and/or C to C alkanonic hydrogen peroxide,and provide such low molecular weight polymers with hydroxyl groups; and(5) this invention achieves other new and useful improvements which willbe apparent from the following general and detailed descriptions ofillustrative embodiments of the invention.

The polymers prepared by the new process are useful as resin and/orbinder components in protective and decorative coatings and for otherpurposes for which low molecular weight polymers of the class describedare desired.

DRAWINGS The accompanying drawings illustrate certain aspects of theinvention. FIG. 1 to FIG. 9 hereof graphically illustrate the minimumamount by volume of the selected alkanolic and/or alkanonic mutualsolvent-diluent required to form a single phase, Le. a completesolution, for different volumes of 50 percent by weight and in someinstances 90 percent by weight aqueous hydrogen peroxide, each incombination with 100 grams of the selected monomer material. Byincluding the values for water in the figures for any concentration ofaqueous hydrogen peroxide the amount of alkanolic and/or alkanonicmutual solvent-diluent to form a single phase can easily be detennined.Similar graphs can easily be prepared for any of the monomer materials,aqueous hydrogen peroxide concentrations and alkanolic and/or alkanonicmutual solvent-diluent systems described herein. The figures areconcerned with the following single phase systems including:

FIG. I Butadiene- 1 ,3-Aqua H o -lsopropanol FIG. 2 Isoprene-Aqua H OMethanol FIG. 3 Isoprene-Aqua H O Isopropanol FIG. 4 IsopreneAqua'H,OMethyl ethyl ketone FIG. 5 Piperylene-Aqua H O -Jsopropanol FIG.6Styrene-Aqua H o Methanol FIG. 7 Styrene-Aqua H O Isopropanol FIG. 8vinylidene chloride-Aqua H o lsopropanol FIG. 9 Methyl methacrylate-AquaH o lsopropanol FIG. 10 is an infrared spectrum (significant portion) ofthe polybutadiene of Example 67, Table XII GENERAL DESCRIPTION Ingeneral, the present invention resides in the polymerization of (A)monomer material at least 2 percent of which is monomer materialsubstantially insoluble to water, by the formation of a homogeneoussystem including (B) aqueous or anhydrous hydrogen peroxide and (C)liquid organic mutual solvent-diluent for the said hydrogen peroxide andthe monomer (A) and any water present, which mutual solvent-diluentcomprises at least a major proportion of lower aliphatic saturatedoxygenated solvent selected from the alcohols, ether-alcohols,keto-alcohols and ketones and which renders the combination of (B) and(C) homogeneously soluble in the monomer (A) in a proportion appropriateto promote adequately rapid but controllable polymerization of themonomer material in said solution, and heating the same at elevatedtemperatures of above 100 C. to about 200 C. to form polymers which liein the range of from about 500 to about 10,000 number average molecularweight and preferably about 1,000 to about 3,000 number averagemolecular weight; so that the controlled molecular weight polymers asproduced have groups which, except for the polymerized monomer materialtherein, are oxygen containing groups essentially derived from thesolution of said hydrogen peroxide in the said liquid organic mutualsolvent.

The most suitable individual and combined mutual solventdiluents for thehydrogen peroxide and the monomer material are those which formhomogeneous solutions in all proportions, both with aqueous andanhydrous hydrogen peroxide and with the monomer material concerned, andthese include the alcohols, ketones, alcohol-ketones, andalcohol-ethers, which are miscible in water in all proportions. Of thesematerials the alcohols, alcohol-ketones, and alcohol-ethers containalcoholic hydroxyl groups, i.e. carbinol groups.

Also employable as solvent-diluents are (1) those of said liquid organicmutual solvent-diluents which are miscible with water only in limitedproportions, but sufficiently so to produce a single phase of theingredients; (2) those of said liquid organic mutual solvent-diluentswhich arev miscible with water in at least such limited proportions incombination with essentially non-water miscible diluent in suchproportions as to render the combination a mutual solvent-diluent; and(3) azeotropic mixtures of the foregoing which are advantageous forrecovery purposes.

In a first embodiment of the invention, polymers in the above indicatedmolecular weight range of 500l0,000, are produced from vinylidenemonomer material, e.g., styrene, in which aqueous hydrogen peroxide isvirtually insoluble. If the monomer material is merely mixed withaqueous hydrogen peroxide then two phases result and only a very smallamount of solid polymer is produced at the interface between them.However, when in accordance with the present invention, there iscombined, with an appropriate amount of hydrogen peroxide, anappropriate proportion of such liquid organic mutual solvent-diluent,then this combination when added to the styrene fonns a clearhomogeneous solution therewith, and at elevated temperatures, i.e. above100 C., polymerization is initiated which can ,be controlled to maintainthe polymerization temperature, e.g. at l 15? C. to obtain in say 3 to 4hours a conversion of from about 40 percent to about percent of themonomer to polymer. The product, when freed of unreacted and residualmaterials, is a clear water-white polymer, e.g. polystyrene. Thus, thisembodiment of the invention provides homopolymers of vinylidene monomerswhich contain groups derived from the mutual solvent solution ofhydrogen peroxide (the term vinylidene monomers as used herein excludesconjugated diene monomers, drying oil substances, and othernon-conjugated polyene materials). In this first embodiment, similarlycharacterized interpolymer of such ingredient monomers may be produced,e.g. vinyl chloride/vinyl acetate interpolymers', styrene/acrylonitrileinterpolymers, and interpolymers with dyeable groups. In this firstembodiment of the invention there may be employed as the liquid organicmutual solvent-diluent an azetropic mixture of a mutual solvent-diluentand a solvent for either the monomer material or the hydrogen peroxidethus facilitating separation and recovery of the mutual solvent-diluentfrom the polymer.

In a second embodiment of the invention, polymers in the molecularweight range of 500 to 10,000 are produced from ethylenicallyunsaturated monomer material which contains a significant proportion,e.g. from 2 to 100 percent, of conjugated diene monomer material, e.g.,butadiene-l,3, in which hydrogen peroxide is virtually insoluble. If themonomer material is merely mixed with aqueous hydrogen peroxide then twophases result and when heated 2 hours at 120 C. only a very small amountof solid polymer is produced at the interface betweenthem. I-Iowever,when, in accordance with the present invention, there is combined, withan appropriate amount of hydrogen peroxide, an appropriate proportion ofthe liquid organic mutual solvent-diluent, then this combination whenadded to the monomer material comprising conjugated diene monomer, formsa clear homogenous solution therewith, and at elevated temperatures,e.g. some several degrees above 100 C. polymerization is initiated whichcan be controlled to maintain the polymerization at desired temperatureswithin the range of above to 200 C., to obtain, in e.g. 3 to 4 hours, aconversion of from about 40 percent to about 60 percent of the monomerto polymer. The product thus produced from butadiene-1,3, when freed ofunreacted and residual materials, is a clear water-white viscous liquidpolymer, predominately of 1,4-configuration, which contains groupsderived from the mutual solvent solution of hydrogen peroxide. Followingthe same practice with other conjugated diene monomer combinations,produces homopolymers and interpolymers respectively of similarcharacteristics and hydroxyl functionality. In this second embodiment ofthis invention, interpolymers especially in the above indicatedmolecular weight ranges may be produced from conjugated diene monomersand vinylidene monomers. When the vinylidene monomer is in minorproportion, such as about 2 percent by weight of the monomers charged,brilliantly clear water-white viscous liquid polymers are produced,e.g., when employing butadiene-l,3 with about 2 percent as comonomer ofvinyl acetate, or of methyl methacrylate, or of methyl acrylate. In thissecond embodiment of this invention, liquid interpolymers may beproduced from conjugated diene monomers and aromatic hydrocarbon vinylmonomers e.g. butadiene-l ,3 and styrene or the vinyl toluenes.Especially when the aromatic hydrocarbon vinyl monomer is charged inless amount, after the polymerization of the hydrocarbon conjugateddiene monomer has been initiated, interpolymers are obtained which areclear, water-white, viscous liquids. In this second embodiment,interpolymers of conjugated diene monomers with polar vinylidenemonomers may be produced, e.g., with vinyl chloride, vinyl acetate,acrylonitrile and monomers producing interpolymers with dyeable groups.In this second embodiment of the invention there may be employed as theliquid-organic mutual solvent-diluent an azeotropic mixture of a mutualsolvent-diluent and a solvent for either the monomer material or thehydrogen peroxide thus facilitating separation and recovery of themutual solvent-diluent from the polymer.

DEFINITIONS As used herein, the term interpolymers" comprises theproducts produced by batch, continuous or intermittent polymerization inwhich a single monomer is polymerized in the presence of another polymermaterial or in which two or more monomers in the absence or presence ofother polymer material are at least in part simultaneously,intermittently, or sequentially charged and simultaneously,intermittently, or sequentially polymerized; or in which theinterpolymer is formed by a combination of these modes ofpolymerization; and when the components of an interpolymer areinseparable from one another, because chemically bonded to one another,

then the polymer may be referred to to as a copolymer, block polymer orgraft polymer as the case may be.

As used herein, the term ethylenically unsaturated monomer" denotes amonomer preferably of not more than 14 carbon atoms and containing andpolymerizable through at least one group with the aid of hydrogenperoxide, includes vinylidene monomers, includes conjugated dienemonomers having the group (but not the non-conjugated diene monomers),and excludes drying oil substances as hereinafter defined, and excludesother non-conjugated polyene compounds. The term vinylidene monomerdenotes an ethylenically unsaturated monomer containing but one groupand includes vinyl" monomers having but one CH CH- group. The termdrying oil substances connotes (1) the drying oils, especially thosecontaining conjugated unsaturation e.g., tung oil, oiticica oil, isanooil, conjugated linseed oil, conjugated soya bean oils, fish oil, etc.,(2) the air blown or bodied drying oils, whether from conjugated ornon-conjugated drying oils and whether bodied by heat and/orcatalytically, (3) the fatty acids including their dimers, trimers andtetramers derived from such drying or modified drying oils. And the termpolyene as used herein denotes compounds containing two or more groups.

The monomers concerned include several categories of monomers, hereindifferentiated by their relative solubility to water. Since the solventor solute relationships of hydrogen peroxide and aqueous hydrogenperoxide are relatively similar to those of water, the readily availablewater values afford a reasonable basis for classification.

As used here the term monomers virtually insoluble to water denotesethylenically unsaturated monomers which at 20 C. do not dissolve morethan 1.0 gram of water per grams of monomer and comprises two classes ofmonomers: (a) the hydrocarbon monomers virtually insoluble to water and(b) the polar monomers virtually insoluble to water.

The hydrocarbon monomers virtually insoluble to water includehydrocarbon monomers generally, and comprise, but are not limited to,the typical examples set forth in Table A.

TABLE A Hydrocarbon Monomers Virtually Insoluble to Water MonomerSolubility of Water in Monomer l) by weight at 20 C.) HydrocarbonConjugated Diene Monomers, e.g.

Butadiene-l ,3 0.06 Isoprene 0. I Piperylene 0. 1 Hydrocarbon VinylideneMonomers, e.g.

Styrene 0.6 a-methylstyrene 0.8

( l) as reported in literature The polar monomers virtually insoluble towater which include, but are not limited to, the typical examples setforth in Table B, are separately classified because, in addition tocarbon and hydrogen, these monomers contain other constituent materialselected from the group consisting of oxygen, nitrogen, the halogens,silicon and in some instances sulfur and phosphorous atoms, andcombinations of the foregoing.

TABLE B Polar Monomters Virtually Insoluble to Water Solubility of Waterl) as reported in literature (2) wt. solubility in water at 25 C.

As used herein the term monomers substantially insoluble to waterconnotes those polar monomers containing carbon, hydrogen, and otherconstituent material which at 20 C. dissolve over 1.0 grams of water per100 grams of monomer, but not over 3.5 grams of water per 100 grams ofmonomer. Such monomers include, but are not limited to the typicalexamples set forth in Table C.

TABLE C Monomers Substantially Insoluble to Water Solubility of Water inMonomers Monomers l by weight at 20 C.) Methacrolein 1.7 Acrylonitrile3.2 Methyl methacrylate 1.15 Ethyl acrylate 1.5 1 Methyl acrylate 2.32Methyl isopropenyl ketone 3.0 lsopropenyl acetate 1.21

( l as reported in literature As herein used, the term monomersessentially insoluble to water" connotes collectively the monomers whichare either virtually insoluble to water or substantially insolubleto-water as above defined.

The term "monomers soluble to water" as herein used, denotes the polarmonomers which are soluble to water to an extent greater than themonomers essentially insoluble to water. Such monomers include, but arenot restricted to, the typical examples set forth in Table D.

TABLE D Polar Monomers Soluble to Water Solubility l Monomers (g.monomer/I g. water) Acrylamide 204 Acrolein 20.8

( l as reported in literature.

The term hydrogen peroxide as used herein includes aqueous hydrogenperoxide and comprises several distinct categories or ranges of thelatter having different characteristics and utilities as set forth inTable E. For the purposes of this invention categories (b), (c)( l) and(c)(2) in this table constitutes the preferred range, while categories(c)(l) and (c)(2) constitute vthe more preferred non-hazardous range,and category (c)( l constitutes the most preferred range.

The hydrogen peroxide employed may be produced by any of the knownprocesses and may contain small amounts of organic or inorganicimpurities provided such are not deleterious to the stability of thehydrogen peroxide. The mutual solvent-diluent and hydrogen peroxide whenproduced by contacting an isoalcohol e.g. isopropanol with oxygen or airdoes contain an appreciable quantity of ketone, e.g. acetone, whichcombination has been found effective among the catalyst-mutual solventsystems of this invention.

The term terminal groups" as used herein refers to the groups derivedfrom the alkanolic and/or alkanonic hydrogen peroxide, which initiateand/or terminate the polymer molecules and thus provide them withterminal hydroxyl groups.

been used in preparing the examples hereinafter set forth with suchmodifications as are set forth therein, are as follows:

CONIBINING ESSENTIAL INGREDIENTS The essential ingredients employed inthe polymerization recipe are the monomer material, the hydrogenperoxide, and the mutual solvent-diluent therefor. As will beappreciated from Table E above, the process of this invention should becarried out so as to avoid having hydrogen peroxide and organic materialcombined in detonable proportions at any time. Accordingly, whenhydrogen peroxide is employed in the range of category (a), above 80 toover 99 percent hydrogen peroxide, such hydrogen peroxide should beadded to approximately 2 to 3 volumes or'more of the mutualsolvent-diluent, to prepare a safe solution to combine with the monomer;or be prepared in situ by air oxidation of a secondary alcohol; or becombined in more dilute aqueous solution followed by removal of thewater. The amount of mutual solvent-diluent so used must be sufficientto insure that when the resulting solution is combined with the monomermaterial, the combination will form a homogeneous solution or singlephase.

Likewise, in using aqueous hydrogen peroxide of category (b) Table E,while this category is less hazardous, similar precautions arepreferably employed. When the aqueous hydrogen peroxide falls incategories (c)( l) and (c)(2) constituting the preferred range, TableIE, it is immaterial in what order the essential ingredients arecombined, except that a homogenous solution or single phase should beobtained prior to the initiation of polymerization. This same commentapplies to the more dilute substantially ineffective ranges, categories(d)(l) and (d)(2), in which the presence of excessive water andconsequential presence of excessive mutual solventdiluent unduly retardsthe polymerization and overburdens the polymer recovery operation.

For the most part in the examples, 50 percent by weight aqueous hydrogenperoxide from category (c)(l), Table E, has been employed as affordingthe best over all balance of conditions for safe polymerization atelevated temperatures and at adequate polymerization rates, withadequate heat transfer for controlling the temperatures ofpolymerization, and for facilitating handling of the reaction productsand the economical recovery of the polymer therefrom. While the minimumrequirement of mutual solvent-diluent for bringing into single phase thehydrogen peroxide and monomer material to be used can be readilydetermined merely by combining proportionate parts of the hydrogenperoxide phase and monomer phase and measuring the quantity of mutualsolventdiluent required to be added to convert the two phases to asingle phase; for purposes of facilitating control it is preferred toemploy a volume of mutual solvent-diluent at least equal to the volumeof aqueous hydrogen peroxide, and to in any event TABLE E CATEGORIES OFHYDROGEN PEROXIDE H202 Wt. Wt. Caterange percent percent 4 v gory (wt.percent) H202 H2O Moles H2O Characteristics Utilities (a) 99 to 80 E100,80 20, 20 g1.0;0.0,1.0: 0.5 Possibly ex- (a) Hazardous in presence oforganic material when 01. (b) 80 to 54. 2 80, 54. 2 20, 45. 8 1. 0:0.5, 1. 0: 1. 5 plosive range. (b) Hazardous in presence of organicmaterial where at about stoiehiometric proportions. (c) (1) 1 54. 2 to48. 5 54. 2, 48. 5 45. 8, 51 5 1. 0:1. 5,1:2 Non hazardous (c) (1)non-hazardous and highly effective. (0) (2). 48. 5 to 33.1 48.5,33. 151. 5, 66. 9 1: 2, 1:4 Preferred (c) (2) non-hazardous and lessefiective.

range. (d)(1) 33. 1 1.0 15. 9 33.1, 15. 9 66. 9, 84 1 1: 4, 1:10Substantially (d)(1) not practically eiIective. (d)(2) 15. 9 to 6.0 15.9, 6.0 84. 1, l4 0 1: 10, 1:30 ineffective (d) (2) virtuallyineffective.

range.

GENERAL PROCEDURE employ at least 5 ml of mutual solvent-diluent foreach l00 The preferred procedures employed for effecting the grams ofmonomer to be charged.

The proportions of the hydrogen peroxide to be used should be in therange'of 0.5 to 10 grams, preferably 1.0 to 5 grams, and most preferably2.0 to 4 grams, based on hydrogen peroxpolymerizations according to thisinvention, and which have ide ontent, er 100 ram of n e i l harged,

The monomers to be polymerized, more particularly described hereinbeforeand hereinafter, can be charged free of stabilizers and/or antioxidants.in the examples of preparation of polybutadiene according to thisinvention, the monomers are distilled and hence freed of antioxidants.Inexamples employing isoprene "and/or piperylene and/or vinylidenemonomers, however, the monomers used in the examples were not freed ofantioxidants. Thus the invention may be practiced either in the presenceor the absence of antioxidants.

OXYGEN EXCLUSION In the polymerization of vinylidene monomers or ofconjugated dienes with or without vinylidene monomers, the presence ofoxygen is to be avoided, as this may lead to gelling of polymer andfouling of the reactor.

Another source of oxygen which it may be desirable to reduce or controlis that afforded by the catalytic decomposition of hydrogen peroxide perse. 7

To minimize such decomposition in constructing the reactor system foruse in the present process, only materials which do not appreciablydecompose hydrogen peroxide should "be used, such as the types of glass,ceramic ware, tin, aluminum or stainless steel (e.g. 300 type stainlesssteel) suitable for storage of hydrogen peroxide. Thus the inner surfaceof the reaction vessel is preferably constructed of or lined withaluminum or aluminum alloy (i.e. of negligible copper content), tin,stainless steel, glass, enamel, porcelain or like predominantlysilicious material or coated with'a resin or other material in contactwith which hydrogen peroxide is relatively stable. The inner surface ofthe reactor, when composed of glass or like silicious material, may betreated with a suitable compound of boron, such as boric acid, or theinner surface may be enameled. Where the reaction vessel is constructedof or lined with stainless steel, or aluminum, it is desirable topassivate the equipment by known methods, e.g., new equipment ofstainless steel may be and preferably is thoroughly cleaned and thenpassivated by treatment with a strong volatile oxidizing agent,preferably hot to 50 percent by weight nitric acid and hot to 60 percentaqueous hydrogen peroxide in succession.

HYDROGEN PEROXIDE STABILIZERS To further inhibit the decomposition ofhydrogen peroxide during the polymerization reaction there maybeincluded in the recipes hereof in minor amounts one or more hydrogenperoxide stabilizers.

From the foregoing, it will be appreciated that the Present invention,in its broader aspects, may be practiced with -or without hydrogenperoxide stabilizers.

REACTORS AND ADDITION OF MATERIALS THERETO The reactor may be a tubularreactor, or a vessel type reactor with or without agitation and thepolymerization may be carried out batchwise, continuously orintermittently.

The hydrogen peroxide may be added at the beginning of the reaction. Themonomer material may be added before, concurrently with or after theother ingredients as above indicated, or even a part of the monomermaterial may be added after the polymerization has commenced.

MONOMER MATERIAL The monomer materials employable in the practice of theinvention in its several embodiments comprising essentiallyethylenically unsaturated monomers containing one or more groupspolymerizable with the aid of hydrogen peroxide and such monomers inaddition to those mentioned heretofor and in the examples are selectedfrom the following classes of monomers of which the examples .set forthare illustrative: hydrocarbon conjugated dienes such as butadiene-1,3,isoprene, 2,3-dimethylbutadiene-1,3, piperylene, hexadiene- 1,3,2-phenyl-butadiene-l,3, and the like; the polar conjugated dienes suchas land 2-cyano-butadiene-.l,3, 2- ehlorobutadiene-l,3 and the like (itis to be noted that the term conjugated dienes includes hydrocarbonconjugated dienes and polar conjugated dienes); the a-olefin monomers;vinyl,vinylidene and allylaromatic monomers such as styrene, the vinyltoluenes, the methyl styrenes, the ethyl styrenes, the propyl styrenes,the vinyl biphenyis, the vinyl biphenylethers, the vinyl naphthalenes,the a and/or B substituted vinyl aromatics such as a-methyl styrene,isopropenyl biphenyl, isopropenyl biphenyl oxide and the like; thesubstituted vinyl, allyl or vinylidene aromatics including the alkyl,phenyl, alkoxy, phenoxy, acetyl, acylamino, isocyanate, carbamide,

arnido, nitrile, carboxyamido, trifluoromethyl, phosphoro, and

halo (F, Cl, Br) substituents including the mono, di, tri, and tetrachloro styrenes, the fluorostyrenes, the chlorovinyl toluenes, thefluorovinyl toluenes, the cyano styrenes and the like monomers; estersof mono-olefinic acids with saturated alcohols including a and Bsubstituted mono-olefinic acids and including alkyl, aryl, aralkylesters such as the methyl, ethyl, propyl, butyl, isobutyl, pentyl,hexyl, cyclohexyl, phenyl esters of acrylic, methacrylic, ethacrylic,and the like; and including the a-halo-acrylates such as'methyla-chloroacrylate, propyl a-chloroacrylate and the like; the esters ofmono-olefinic alcohols with saturated acids, such allyl, methallyl,crotyl, lchioroallyl, 2-chloroallyl, 'cinnarnyl, vinyl, methylvinyl,lphenylally, butenyl and the like esters of saturated aliphatic andaromatic monobasic acids as vinyl and allyl acetate, isopropenylacetate, vinyl formate, vinyl-2-ethyl hexoate, methyl vinyl acetate,vinyl and allyl propionate'or n-butyrate and isopropenyl propionate,isopropenyl butyrate, vinyl and allyl benzoate, and the like; thedialkyl esters of mono-olefinic dicarboxylic acids such as the dialkylesters and mixed dialkyl esters from such alkyls as methyl, ethyl,propyl, and the like through C of the mono-olefinic dicarboxylic acidsincluding maleic, citraconic, itaconic, muconic, glutaconic, fumaric andderivatives of these .esters such as diethyl chloromaleate and the like;mono-olefinic acid esters of epoxy alcohols, such as 2,3-epoxypropylmethacrylate or acrylate, glycidyl methacrylate, glycidyl acrylate,glycidyl crotonate, 2,3-epoxybutyl acrylate, and the like; mono-olefinicacid esters of fluoro alcohols such as the a-trifluoromethyl acrylicacid esters such as the methyl or ethyl ester or the ester ofperfluoroethanoi or the partially fluorinated alcohols, that is thefluoroalkanols such as octafluoropentanol and the like; themono-olefinic halides, such as vinyl fluoride, vinyl chloride, vinylbromide, vinylidene fluoride, vinylidene chloride, allyl fluoride, allylchloride, a-methallyl fluoride, a-methallyl chloride, a-ethallylfluoride or chloride or bromide, tetrafluoroethylene,trifluorochloroethyiene, dichloridifluoroethylene,trichlorofluorethylene, perfluoropropylene, l-phenyl-1,2dilluoroethylene, trichloroethylene and the like; the monoalkenylketones such as methyl vinyl ketone, isopropenyl methyl ketone, allylmethyl ketone, mesityl oxide, allyl phenyl ketone and the like; themono-olefinic ethers such 'as vinyl ethyl ether, vinyl butyl ether,vinyl cyclohexyl ether, vinyl phenyl ether, vinyl tolyl ether, vinylbenzyl ether, methyl isopropenyl ether, allyl ethyl ether, methallylethyl ether, chloroallyl ethyl ether and the like; the mono-olefinic.aldehydes such as au-olein, methacrolein, crotonaldehyde and the like;the mono-olefinic trlazine monomers including triazlne monomers in whichone of the carbons of the triazine ring is attached to a vinyl, allyl,methallyl, crotyl, l-chioroallyl, 2-chlorallyl, cinnamyhbutenyl radicalor the like and the other carbons of the triazine are attached to cyano,halo (F, Cl, Br), aikoxy, cycloaliphatic (e.g. cyciopentyl, cyclohexyl,etc.), aromatic-substituent (e.g. phenyl, biphenyl, naphthyl, etc.),alkylaryl e.g., tolyl, xylyl, ethylphenyl, etc.) halogenated aromaticand the like; the N- vinyl and 'allyl guanidines including allylmelamine, allyl isomelamine and the like; the N-vinyl-N-alkylguanidinessuch as N-vinyl-N-n-butylguanidine, N-vinyl-N-benzyl guanidine,acryloguanidine, methacryloguanidine and the like; the nvinyl monomerssuch as N-vinylpyrrole, N-vinyl carbazole, N- vinyl-indole, N-vinylsuccinimide and the like; N-vinyl lactams such as N-vinyl caprolactam,N-vinyl butyralactam and the like; the amides and substituted amides ofacrylic acid and a and B-substituted acrylic acids such as acrylamide,methacrylamide, ethacrylamide, N-methacrylamide, N- methylmethacrylamideor ethacrylamide, N,N-bis (hydroxyethyl) acrylamide,N,N-diethylacrylamide, N,N-ethylmethylacrylamide and other monoand di-Nsubstituted unsaturated acid amides where the substituent is C, to Calkyl, alkoxy, haloalkyl and the like; the mono-olefinic nitriles suchas acrylonitrile, methacrylonitrile, ethacrylonitn'le,chloroacrylonitrile and the like; the fluoro-substituted nitriles ofmono-olefinic acids such as N-(2,2,3-trifluoro-ethyl) acrylamide or'methacrylamide, N-(2,2-difluoroethyl) acrylamide or methacrylamide; themono-vinyl pyridines such as 2- vinylpyridine, 3-vinylpyridine,4-vinylpyridine, 2-vinyl-5- ethylpyridine, 2-methyl-5-vinylpyridine andthe other ethyl and methyl isomers of vinylpyridine and the like; thevinyl heterocyclic compounds such as 2-vinyl-furan and 2-vinylthiopheneand the like; the silicon containing monoolefinic monomers such asvinyltrichlorosilane and its hydrolysis products, thevinyl and allylsilicates and the like; the phosphorus containing monomers such asacrylic esters containing phosphonamido groups such asdiamidophosphoroacrylate and the like and other similar polymerizablematerials having a polymerizable unsaturated carbon-to-carbon bond.

MUTUAL SOLVENT-DILUENTS The term mutual solvent-diluents connotes thesolvents for hydrogen peroxide and the selected monomer material and anywater present, and these mutual solvent-diluents are for the most partwater miscible liquid organic solvents also miscible with the monomermaterial and preferably easily separable from the polymer. Most suitableare the liquid mutual solventdiluents selected from the water misciblealcohols, ether-alcohols, keto-alcohols and ketones. Therefor, the C toC alcohols (i.e. alkanolic solvents) are especially suitable andinclude: methanol, ethanol, n-propanol, isopropanol, n-butanol,isobutanol, sec-butanol, tert-butanol. The ketones (i.e. alkanonicsolvents) which may be used include: acetone, methyl ethyl ketone, andthe like, the C to C ketones being preferred. The ketone alcoholsincluding diacetone alcohol may be used; also the ether-alcoholsincluding 2-methoxyethanol, 2-(ethoxyethoxy)ethanol and the like.Furthermore these mutual solvents may be used in combinations with eachother and with other diluents as set forth heretofor especially inazeotropic mixtures, preferably those in which the mutualsolvent-diluent predominates, e.g., methanol/Z-butanone 70/30,methanol-1,2-dimethoxyethylene 90/ 10, methanol/toluene 69/31,ethanol/1,l-dichloropropane 53/47, ethanol/perchloroethylene 61/19,ethanol/toluene 68/32, isopropanol/tetrachloroethylene 80/29,isopropanol/toluene 69/31, n-propanol/toluene 52.5/47.5, and the like.Also there may be employed aqueous azeotropes of the mutualsolventdiluent and such azeotropes may be economically recovered andrecycled. Thus it can be seen that the mutual solventdiluent preferablyshould comprise at least a major proportion of lower aliphatic saturatedoxygenated solvent.

CONDITIONS As above indicated the reactions hereof are conducted inliquid phase at elevated temperatures sufficiently above C., to initiateand maintain polymerization and preferably above C., with or without avapor space depending on whether the reactions are conducted batchwiseorcontinuously. At these temperatures the containing vessel may be subjectto considerable pressure, e.g. 400-500 psi. for butadiene-1,3polymerization, and for other more volatile materials employable inaccordance with this invention the pressures may range upward to severalthousand pounds per square inch, e.g. 5,000 to 8,000 psi. forcopolymerization of butadiene and ethylene. As all of thesepolymerization reactions are exothermic, it is important that thereaction systems chosen have adequate heat transfer in order to avoidrun-away reactions. The time of polymerization may vary with thematerials and temperatures employed, and may range from about one-halfhour to 5 hours or more, a time of from 1 to 3 hours usually beingsufiicient to obtain an adequate conversion of monomers at selectedtemperatures, as illustrated in the adjoined examples. Control of theaging of the unsaturated polymer product in the presence of the residualor added hydrogen peroxide and/or mutual solvent before or afterstripping of the monomers and/or solvents, which may be expedited byheating, efifects control of the oxygen content, more particularly thehydroxyl content, of the polymer product.

Typical stripping procedures referred to in the earlier examples, suchas vacuum and heat with or without steam, were employed in the examplesthroughout and exemplify any suitable way of recovering the polymerproduced.

EXAMPLES The following examples will serve to illustrate the inventionin more detail:

EXAMPLES 1 THROUGH 4 1n the examples 1 through 4 of Table l wereemployed 4 glass bottles each containing 3 ml of aqueous 50 percent byweight hydrogen peroxide and to 3 of these bottles were addedrespectively 1 ml, 2 ml and 3 ml of water and further to each of the 4bottles were added 45 ml of isopropanol (the mutual solvent-diluentabbreviated as M-S-D) and 25 grams of butadiene-1,3. The bottles werecapped and placed in a steam pressure chamber and held at 110 C. for 3hours. After cooling the bottles were opened and from the polybutadienetherein was removed the volatiles e.g., butadiene-1,3, butadiene dimer,isopropanol, acetone, residual hydrogen peroxide, water etc. and thiswas accomplished with the aid of heat and vacuum, followed by steam andvacuum. The resulting products were clear, colorless, viscous liquidpolybutadienes. For a tabulation of the ingredients employed,polymerization conditions and polymer yield for examples 1 through 4,see Table l hereafter. V

These examples l through 4 teach that aqueous hydrogen peroxidethroughout the concentration range of 25 to 50 percent can be employedwith little appreciable change in polymer yield provided the quantity ofmutual solvent-diluent FEE qons nt TABLE I.LIQ,UID POLYBUIADIENE [Effectof aqueous concentration of hydrogen peroxide on butadiene conversion]Hydrogen EXAMPLES thru 8 Example 5, Table II shows that low yields ofrubbery polymer are obtainedwhen no mutual solvent-diluent is employed.Example 6, Tablell, shows that when the volume of mutual solvent-diluentemployed is equal to the volume of aqueous hydrogen peroxide then theyield of polybutadiene is almost doubled when compared with example 5 inwhich no mutual solvent-diluent was employed. In example 7, Table II,when sufficient mutual solvent diluent was used to insure'that a singlehomogeneous phase existed and in this example the polymer yield wasincreased 4 fold when compared with the polymer yield of example 5 inwhich no mutual solvent-diluent was used. In example 8, Table II, themutual solvent-diluent was employed in amounts further exceeding theamount of monomermaterial and this excess mutual solvent-diluent showedlittle effect when compared with example 7 Table EXAMPLE 9 TllROlJGl-l17 Alcohol as mutual solvent-diluent has been employedin examples 9-17,Table III. The conversion obtained with these C to C water misciblealcohols is' ofv the same order of magnitudetherefor in selecting analcohol other'factors are considered such. as price considerations,stability of'the alcohol to o'xidatiomcffect of the alcohol on molecularweight of the "polymer, solubility of the polymer insuch alcoholicsystems conditions andpolymer yields for examples'9 through 17 see TABLEIII Liquid Polybutadiene [Effect of various alcoholicmutual-Solvent-diluents on butadleno conv.]

Hydrogen Monomer peroxide, Polymerization Polybutadienc material, 50%wt. M-S-D alcohol butadiene-1,3 aqueous Temp, Time Yield ViscosityExample No. (grams) (ml.) Type M1. C. (hrs.) (grams) (Gardner) 100 6Methanol. (i0 115-120 3 72 Z-6 100 6 Ethanol 60 115-120 3 70 Z-fi 100 *6d0 60 115-120 3 70 Z-fi 100 *6 n-propauoL. 60 115-120 3 76 Z-6 100 6Isopropanol- 60 116-120 3 72 Z-G 100 (i n-butanol** 60 115-120 3 66Z-4-5 100 0 sec.-butano1- 60 115-120 3 60 Z-6 100 6 t-butan0l 60 115-1203 68 Z-G 100 *6 do 60 115-120 3 62 Z-(i *The aqueous hydrogen peroxidewas first combined with the alcohol and then shaken with anhydroussodium sulfate to remove substantially all of the water thus producingan anhydrous hydrogen peroxide the limiting value of category .(a) TableE.

In place 01 the n butanol may be substituted 2-methyl-1-propanol.

In all the examples 5 through 8 the polymer was freed of volatilematerial, e.g. butadiene-l,3, butadiene dimer, isopropanol, acetone,residual hydrogen peroxide, etc. and this was accomplished with the aidof heat and vacuum followed by steam and vacuum. Products of examples 7and 8 were colorless, viscous liquid polybutadienes. For a tabulation ofthe ingredients, conditions and polymer yields for examples 5 through 8,see Table II hereafter.

in short, conjugated hydrocarbon diene and aqueous hydrogen peroxidewhen combined form a .two phase system and when polymerized at elevatedtemperatures give low yields of a rubbery polymer containing insolublematerial. In contrast when mutual solvent-diluent is employed accordingto this invention one obtains lower molecular weight polymers, free ofinsoluble material, in satisfactory yields.

TABLE II.LIQUID VPOLYB-UTADQIENE [Eflect oi mutual-solvent-diluentconcentrations on butadiene conversion] EXAMPLES 18 THROUGH 28 Theeffect of various mutual solvent-diluents on the polymerization ofisoprene is set forth in examples 18 through 28, Table VII. Theseexamples illustrate a range of mutual solvent-diluents which can'beemployed with isoprene as well as the other monomers set forth undermonomer material herein especially aqueously miscible alcohols, ketones,keto-alcohols, etc.

For a tabulation of the ingredients employed, polymerization conditions,polymer yields, for examples 18 through 28, iIFllQ 1 hete mfier-Hydrogen peroxide, Polybutadiene Monomer M-S-D- aqueous Polym material,isoproerization, Insol- Examplo butadienepanol Percent temp., C./ Yieldubles Viscosity number 1,3(grams) (ml) wt. 11.02 Ml. t1rne,11ours(grams) (grams) (Gardner) 5 100 *6 120/2 12 1.8 Rubbery. 6 100 6 *6120/2 20.8 0.1 Semirubbery 7 30 50 6 120/2 44 0.0 Z-4 8 100 106 60 0120/2 42 0.0 Z-fi Two phase system before polymerization initiated.Single phase system before polymerizatlon imtiated.

TABLE IV.LIQ,UID POLYISOPRENE [Ellect of mutual-solvcnt-diluent type onisoprene conversion] Hydrogen Polyisoprene Monomer peroxidePolymerization material 50% wt. M-S-D Conver- Example isoprene aqueousTemp. Time Yield sion (per- Rel. index number (grams) (ml.) (type) (mL)0.) (hrs) (grams) cent wt.) ND 21 25 1. 5 Methanol 20 4 13. 5 54 1. 515725 1. 5 Ethanol 15 110 4 14. J 60 1. 5161 25 1.5 n-lropanol 12 110 415.2 61 1. 5101 25 1. 5 Isopropanol. 12 110 l 14. 8 50 1. 5168 25 1. 5n-Butanol. 25 110 4 15.0 00 1. 5170 25 1. 5 20 110 4 14. d 57 1. 5. (Si)25 1.5 liutyl Cellosolve 14 120 4 20.6 82.5 1. 515!) EXAMPLES 46 AND 47In examples 46 and 47 Table V11 butadiene-l ,3 and styrene together witha small amount of a polar monomer is interpolymerized with aid ofhydrogen peroxide and isopropanol as t zsmyt aliz yat-s l ek.

For tabulation of ingredients employed, polymerization conditions andliquid polymer yields for examples 46 and 47,

Examples 40 to 45, Table VI illustrate the interpolymerization with theaid of hydrogen peroxide of isoprene and vinyl acetate employing asmutual solvent-diluent acetone, methylethyl ketone and isopropanolrespectively. In example e e Table V hereinafter. see Table VI!hereinafter.

' TABLE V.-LIQUID P OLYPIPERYLENE [Efiect of mutual-solvent-diluenttypes on piperylene conversion] V Polypiperylene Hydrogen peroxidePolymerization Conver Monome 50% Wt. M-S-D sion Rel.

Example piperylene aqueous Temp. Time Yield (percent index number(grams) (ml.) Typo M1. 0.) (hrs) (grams) wt. ND

25 1.5 Methanol 50 110 8 8.1 32 1. 6000 25 1.5 Ethanol. 50 110 8 11.6 381.4997

25 1. 5 n-Butanol. 75 110 8 10. S) 44 1 4990 25 1. 5 IsobutnnoL 110 8 739 l. 4901 25 1.5 L-ll utunoL 25 110 8 J. 7 3.) 1. 5001 25 1.5 n-Amylalcohol. 50 110 8 10. 5 42 1. 4088 25 1. 5 iso-Amyl alcohol. 50 110 810. 5 42 1. 4984 25 1. 5 Acetone 25 110 8 8.1 32 1. 4094 25 1.5 Methylethyl ketone 50 110 8 7.0 28 1. 5000 EXAMPLES 40 THROUGH TABLE VIIlnterpolymers from Butadi'ene and Vinylidene Monomers Example No. 46 4745, Table VI an mterpolyrner 18 prepared of piperylene, Monomer Materialstyrene and a-methyl styrene. 40 Acryloni rile, ml. 0.5

For tabulation of ingredients employed, polymerization gifiggi g 18 gconditions and liquid polymer yields for examples 40 through g l g 2 3245, see Table VI hereinafter. M S D lsopropanol, ml. 15 15 HydrogenPeroxide TABLE VI 45 wt. aqueous, ml. 2 2 P l t' [Interpolymers of eonugated drones and vmyhdone monomers] gggti g 1 5 I l 5 Example Number 4041 42 43 44 45 Tlme- 2 2 lnterpolymer Monomer material: Yield, g. 44 46i prene, g 50 50 5O Viscosity(gardner) Z-6 Z-6 "gi l G 2. 4 EXAMPLES 48THROUGH 51 47 45 In examples 48 through 51 Table V111 with the aid ofaque- 0 65 25 m 5 55 ous hydrogen peroxide and as mutual solvent-diluentHydmgen Peroxide: iso ro anol exce t exam le 51 which em 10 s acetone50% wt.aqueous,ml 3 3 3 3 3 1.7 p p p p y Polymerization. isoprene ISmterpolymenzed with various vmyhdene including emp., 110 110 110 11 11 2vinyl monomers.

2 f; 13 tabulagqn mfmdlemslfiployed, y z Yjelr 1,' 7 con itions an iquipo ymer yie s or examp es t roug Viscosity, (Gard er) Z-b -fi -fi H 51Table VH1 hereinafter TABLE VIII [Interpolymers of isoprene andVinylidene monomers] Hydrogen M-S-l) Interpolymer peroxide one phasePolymerization ()ther monomer 50% wt. isopro- Conversion Examplelsoprene aqueous panol Temp. Time Yield (percent number (grams) TypeGrams (ml.) (ml.) C.) (1115.) (grams) wt.)

25 Methyl isopropenyl ket0ne 25 1. 5 8 120 4 37 30 25 Methaerolein 25 1.5 10 120 4 30 25 Aerylonitrile 25 1. 5 8 4 32. 3 72 25 d0 8 1. 5 20 1204 22. 5 U0 Acetone.

EXAMPLES 52 THROUGH 55 In examples 52 through 54 Table IX, butadiene-1,3is interpolymerized with 2-vinyl pyridine with the aid of hydrogenperoxide and a mutual solvent-diluent isopropanol. Example 55 is aninterpolymer of isoprene and 2-vinyl pyridine. Polymers from examples 54and 55 can be made water soluble with the aid of acid e.g. phosphoricacid.

For tabulation of the ingredients employed, polymerization conditionsand polymer yields for examples 52 through 55 see Table IX hereinafter.

TABLE 1X Interpolymers from Vinyl Pyridine Example No. 52 53 54 55Monomer Material 2-Vinyl Pyridine, g. 5 9 12.5 12.5

Butadienel ,3, g. 20 16 12.5

lsoprene, ml. 18 M S D lsopropanol, ml. 9 8 8 8 Hydrogen Peroxide 50%wt. aqueous, ml. 1.5 1.5 1.5 1.5 Polymerization Temperature, C. 120 120120 120 Time; hours 2 2 2 3 lnterpolymer Yield, g. 16.4 18.4 23.5 19.1

EXAMPLES 56 AND 57 In examples 56 and 57 isoprene is polymerized withaqueous hydrogen peroxide and mutual solvent-diluent composition; forexample 56 is employed the mixture boiling at 80.6 C. which is theazeotrope consisting of 31 percent by weight toluene and 69 percent byweight isopropanol and for example 57 is employed the mixture boiling at63.8 C. which is the azeotrope consisting of 28 percent by weighttoluene and 72 percent by weight methanol. In place of the constantboiling azeotrope mutual solvent-diluent mixtures set forth in examples56 and 57 may be used other azeotropic mixtures of two or more mutualsolvent-diluents or of mutual solvent-diluents and solvents for themonomer, material only e.g. toluene, benzene, ethyl benzene,methylchloride, etc., or for the hydrogen peroxide; provided of coursethe azeotrope combination is itself a mutual solvent-diluent for boththe monomer material and the hydrogen peroxide, as will be appreciatedby one skilled in the art.

For tabulation of the ingredients employed, polymerization conditionsand polymer yields for examples 56 and 57 see Table X hereinafter.

TABLE X Mixed Mutual Solvent-Diluent Forming Azeotropic Boiling MixtureIn these examples 58 through 61 Table Xl isoprene is polymerized withthe aid of a mutual solvent-diluent and aqueous hydrogen peroxide and astabilizer for the latter. When polymerizing conjugated diene monomerslike butadiene-1,3, isoprene and piperylene including interpolymers ofthese it is important that the hydrogen peroxide should remain stableand not release oxygen which can'gel the polymer at elevatedpolymerization temperatures especially at the metal surfaces of thereactor. In examples 58 through 61 various stabilizers for aqueoushydrogen peroxide have been added and the conversion of isoprene topolyisoprene determined.

For tabulation of the ingredients employed, polymerization conditionsand polymer yields for examples 58 through 61 see Table X I hereinafter.

Table X11 illustrates typical polybutadienes prepared in accordance withthe present invention for which the number average molecular weightswere determined by depression of melting point. Example 63 illustratesthat when the mutual solvent-diluent selected is methanol, then themolecular weight of the polymer is lower. Thus, by a combination of theuse of methanol, especially in amounts greater than required to form asingle phase with the monomer material and aqueous hydrogen peroxide,and the use of greater quantities of hydrogen peroxide to providehydroxyl groups, the molecular weight will be reduced below a numberaverage molecular weight of 1,000 and even to the value of 500 orthereabouts.

Conversely by introducing the aqueous hydrogen peroxide in smallportions, or continuously, throughout the course of the polymerizationand employing a mutual solvent-diluent composition which is a goodsolvent for the polymer formed, the molecular weight may be increased tovalues of the order of 5,000 to 10,000. 7

Example 66, Table X11 is a copolymer of butadiene and styrene preparedwith t.-butanol as the mutual solvent-diluent, and having a weightaverage molecular weight of about 1,400, indicating the effectiveness ofthe tertiary alcohol solventdiluent.

Example 67, Table Xll, yielded a polybutadiene typical of the polymersproduced at least in part from hydrocarbon conjugated dienes inaccordance with this invention. The infrared spectrum of thispolybutadiene of example 67 in the significant range of 10 to 15 micronwavelengths is set forth in FIG. 10, and shows a structure predominately(about percent) of 1,4-configuration, which in turn is predominately oftrans 1,4-configuration (i.e. about percent trans), with only the minorremaining portion being of cis 1,4-configuration.

Likewise, the infrared spectrum of the liquid copolymer of example 66showed the same predominate proportion of trans 1,4-configuration forthe diene derived portion of the interpolymer. This characteristic ofthe new polymers clearly distinguishes them from liquid polybutadienesand butadienevinyl copolymers prepared by alkali-metal polymerizationand the like; for example, the Enjay Polymer MD-420, (produced byStandard Oil Company of New Jersey) a butadiene-styrene copolymercontaining 10-20 percent styrene, has an infrared spectrum indicative ofa structure which is predominately of 1,2-configuration (i.e. 70 percent1,2-configuration) and which contains only a minor proportion of1,4-configuration (i.e. about 10 percent) with the remainder consistingof styrene units.

Similarly the unsaturated polymers of the present invention, which arepolymers of the aforesaid configuration with quite low molecularweights, are quite distinct from the butadiene polymers and copolymersand the like produced by emulsion polymerizations, which are typicallycharacterized, inter alia, by being solid polymer of relatively highmolecular weights.

TABLE XII Molecular Weight Examples Example no. 62 63 64 65 66 67*Monomer material Butadiene-l ,3, g. I 100 100 I00 80 I00 Styrene, g. 20Mutual solvent-diluent Isopropanol, ml. 35 35 35 Methanol 38 Ten.Butanol 40 30 Hydrogen Peroxide 50% wt. aqueous,

ml. 4.15 2 2 2 3 3 Polymerization I Temp,C. 115 110 H 120 115 120 Time,hours 3 4 3 7.5 2 2 Polymer Yield, g. 55 45.5 57 70 37.3 48 Polymerproperties Molecular weight (I) 1600 1800 2300 2500 1400 Intrinsicviscosity( 2) 0.26 0.15 0.27

( l M, by freezing point determination in benzene 2) dilute solutionviscosity For infrared spectra see FIG. I0.

CONTINUOUS POLYMERIZATION While the foregoing examples I through 67 werefor the most part performed by batchwise polymerization, the inventioncan be adapted for continuous polymerization, and as above noted suchcontinuous polymerization has advantages not only from theproceduralstandpoint but also from the standpoint of productcharacteristics. Such adaptation may conveniently be effected inaccordance with the following typical examples 68 and 69.

EXAMPLE 68 For effecting a continuous polymerization in this example wasemployed a single, jacketed, cylindrical high-pressure tube of 3 inchinternal diameter and feet long, with hot water of about 1 l3 C. underpressure circulated at 50 gallons per minute through the jacket; whichmaintained the polymerization temperature in the center of the tube atabout 1 l5 C. The reactants were pumped into one end of the tube by ahigh pressure positive displacement pump and the product was dischargedat the remote end of the tube through a relief valve set at 500 p.s.i.The charge was prepared as follows: to each 1,400 grams of isopropanolwas added 226 ml. of 50 percent by weight aqueous hydrogen peroxide,followed by 4,000 grams of butadiene-1,3.

In this example the butadiene-1,3 had been distilled to remove inhibitor(although such distillations is not required, as is shown by example69). The resulting homogeneous solution or single phase was cooled andpumped to the reactor at the rate of 870 ml. per hour. The reactoreffluent was first stripped of butadiene, and then with the aid of heatand vacuum the isopropanol and small amounts of acetone formed therefromwere removed, and the polybutadiene was then .freed of butadiene dimer,water, and traces of hydrogen peroxide with the aid of vacuum and steamstripping. A 3,193 gram sample of the reactor effluent yielded 1,026grams of polymer, which represented a butadiene conversion of 45percent. The polymer was a water white viscous liquid having a Gardnerviscosity between Z-5 and Z-6'.

EXAMPLE 69 Using a reactor comprising two of the tubes according toexample 68, heated as therein set forth, and connected in series with asingle relief valve at the discharge end of the second tube, there isprepared and supplied to the inlet end of the first tube a charge of thefollowing proportions: to each 892 grams of isopropanol are added 150ml. of 50 percent by weight aqueous hydrogen peroxide, followed by 2,550gramsof butadiene-l ,3 (undistilled), the charge being pumped to theinlet of the first tube at such rate as to provide an average residencetime in the first tube of 2 hours. To the said charge passing from thefirst tube to the second tube is added, by pumping, a supplementalcharge prepared as follows: to each 158 grams of isopropanol is added 25ml. of 50 percent by weight aqueous hydrogen peroxide, followed by 450grams of styrene, the styrene-containing single phase feed beingsupplied in the proportion of 670 grams to each 3,600 grams of thebutadienecontaining single phase feed. The polymer containingeffluentfrom the 500 p.s.i. discharge valve is stripped as in the previousexample (with the unreacted styrene also being removed by thesteam-vacuum stripping) to product a water white viscous interpolymer ofbutadiene and styrene of about l 5 weight ratio, in about 75 percentyield based on the weight of monomers charged.

While for convenience and simplicity in the present example, onesupplemental charge is fed at about the mid position that is between thetwo tubular reactors connected in series, the invention furthercontemplates the employment of additional and/or different supplementalcharges and the introduction thereof at other and different locations,as desired. By proper supplemental feeds of monomer streams, hydrogenperoxide and mutual solvent-diluent or other diluent streams, and withor without modifiers, substantial flexibility of processing may beeffected.

While for examples 68 and 69 tubular reactors are employed, theinvention is not limited thereto, and continuous polymerizations may bepracticed in other forms of continuous reactors, for example, in aseries of stirred pot reactors.

To the polymer materials of this invention having residual unsaturationmay be added antioxidants either before or after stripping, however, theuse of antioxidants has not been found essential when the polymerproducts are stored in air-tight containers.

The residual monomers, the selected single or mixed mutualsolvent-diluent and the hydrogen peroxide can be removed with the aid ofheat and vacuum, and/or may be destroyed chemically as-by treating withformaldehyde.

EXAMPLES 70 THROUGH 74 In examples 70 through 74, Table XIII variousvinylidene monomers are polymerized with the aid of aqueous hydrogenperoxide and the mutual solvent-diluent isopropanol. The vinylidenemonomers containing only a single unsaturated group are polymerized atabout C. and even higher temperatures can be employed especially wherelower molecular weight polymer products are desired. The products ofthese examples were solids.

For tabulation of the ingredients employed, polymerization conditionsand polymer yields for examples 70 through 74, see Table XIIIhereinafter.

' TAB LE XIII [Polymers from vinylidene monomers] Hydrogen Polymerperoxide M-S-D Polymerization Monomer material (50% wt. (isopro-Conversion Example aqueous) pauol) Temp. Time Yield (percent number(Type) (ML) (ml.) (ml.) C.) (hrs.) (g.) wt.)

70 Styrene 25 1.5 *10 120 4 24.9 99.6 25 l. 5 *5-1-3 120 4 17. 6 70. 4

71 Vinyl acetate- TABLE XIII -Cntinued Hydrogen Polymer peroxide M-S-DPolymerization Monomer material (50% wt. (isopro Conversion Exampleaqueous) panol) Temp. Time Yield (percent number (Type) (ML) (ml.) (ml.)0.) (hrs.) (g.)- wt.)

72 Ethyl methaerylate. 25 1. 7+1 120 4 24.0 96 73 Acrylonjtrile 25 l. 5*3+5 120 4 17. 1 68. 4 74 Acrolein 25 1. 5 *8 120 4 14. 4 57. 6

To produce single phase. v M

EXAMPLE 75 Temp. C. 120 120 Example 75 is of a homopolymer of 2-vinylpyridine. 33 5 5331; 3 3 Polymers according to example 75 can be madewater soluble yield, 25 24] with the aid of acld e.g. phosphoric acld.

For tabulation of the ingredients employed, polymerization EXAMPLE 7condltlqns and polymer yield for example 75 see Table XIV Example 78Table XVI, is an example of polystyrene herema prepared in accordancewith the present invention which has 3 TABLE XW number average molecularweight of about 2,000, and which o y from polar Monomers is recovered asa solid powder, and has particular utility for Example Na 75 purposesfor which a low molecular weight polystyrene is Monomer Materialdesired. 2-Vinyl Pyridine, g. 25 TABLE XV] M- s o lsopropanoh 8Molecular Weight Examples Hydrogen Peroxide 50% wt. aqueous, ml. 1.5Example N0. 78 Polymerization Monomer Material Temp., C. 120 Styrene, g.100 Time, hours 3 Mutual Solvent-Diluent lnterpolymer Isopropanol, ml.Yield, g. 24.7 Hydrogen Peroxide wt. aqueous, ml. 3 EXAMPLES 76 AND 77Polymerization Example 76, Table xv exemplifies how styrene can be 35 lfgjif polymerized with the aid of aqueous hydrogen peroxide and a pmutual solvent-diluent composition consisting of the 80.6 C. Ifield, g.P I00 o ymer ropertles bolllng azeotrope of the composition 31 percentby weight Molecular weigh I) [900 toluene and 69 percent by weight,isopropanol. in example 77 again styrene is polymerized with the aid ofaqueous hydrogen peroxide and a mutual solvent-diluent compositionconsisting of the 55.5 C. boiling azeotrope of 88 percent by weightacetone and i2 percent by weight methanol. in place of the constantboiling azeotrope mutual solvent-diluent mixtures set forth in examples76 and 77 may he used other azeotropic mixtures of two or more mutualsolventdiluents or of mutual solvent-diluents and solvents for themonomer material only e.g. toluene, benzenes ethyl benzene,methylchloride, etc., provided of course the azeotrope mutual solventwith or without diluent combination is itself a mutual solvent-diluentfor both the monomer material and the hydrogen peroxide, as will beappreciated by one skilled in the art.

The'use of an alkanolic and/or alkanonic mutual solvent and a solventfor the styrene polymer such as benzene in quantities which formazeotropic boiling mixture, and using hydrogen peroxide as the catalyst,provides a very suitable means of obtaining polystyrene in a solutionform which can readily be foamed to produce polystyrene foam.

For tabulation of the ingredients employed, polymerization conditionsand polymer yields for examples 76 and 77, see Table XV hereinafter.

Polymerization l M by freezing point determination in benzene lnexamples 1 through 78 hereof have been described processes ofpolymerizing and interpolymerizing ethylenically unsaturated monomermaterial of the type specified herein, with the aid of hydrogen peroxide(with or without hydrogen peroxide stabilizers) and a liquid organicmutual solventdiluent of the type specified herein with or without otherdiluents, and in these examples it is to be understood that othermonomer materials as set forth under monomer material herein may besubstituted for the monomers employed and the amount and strength of thehydrogen peroxide may be adjusted to give satisfactory polymerizationrates and depending on the monomer material and the amount andconcentration of hydrogen peroxide employed an amount and kind of mutualsolvent-diluent must be used sufficient to afford a single phase beforepolymerization commences as will be appreciated by one skilled in theart taught by the examples hereof and the description of the invention.

While there have been described herein what are at present consideredpreferred embodiments of the invention, it will be obvious to thoseskilled in the art that modifications and changes may be made withoutdeparting from the essence of the invention. It is therefore to beunderstood that the exemplary embodiments are illustrative and notrestrictive to the invention, the scope of which is defined in theappended claims, and that all modifications that come within the meaningand range of equivalency of the claims are intended to be includedtherein.

We claim:

1. A method for forming a polymer material having terminal hydroxylgroups and a number average molecular weight in the range of from 500 to10,000, which method comprises:

A. forming a single phase polymerization system of a combination of l.monomer material consisting essentially of one or more polymerizableethylenically unsaturated monomers, at

least one of which has one or more substituents other than hydrogen,said monomer material consisting essentially of from 2 to 100 percent byweight of material having a water solubility at 20 C. of no more than3.5

weight percent and from to 98 percent by weight of material having awater solubility at 20 C. greater than 3.5 weight percent, saidethylenically unsaturated monomer materials being selected from theclass of ethylenically unsaturated compounds which excludes the dryingoil substances and the non-conjugated polyene compounds which are otherthan drying oil substances,

. between 0.5- parts by weight of hydrogen peroxide per 100 parts ofmonomer,

a liquid organic mutual solvent-diluent for all the monomer materialpresent and said hydrogen peroxide and any water present, said liquidorganic mutual solvent diluent comprising at least a major proportion oflower aliphatic saturated oxygenated solvent selected from the classconsisting of the water miscible alcohols, ether-alcohols, keto-alcoholsand ketones, said system being essentially free of oxygen and ofcomponents that decompose hydrogen peroxide to form oxygen at less than100 C., and

B. heating said system at sufficient temperatures in the range of fromabove 100 C. to about 200 C. for a sufficient time to initiate andeffect polymerization.

2. A method according to claim 1, wherein at least the major proportionof the liquid organic mutual solvent is selected from those of saidclass of solvents which contain alcoholic hydroxyl groups.

3. A method according to claim 1, wherein at least the major proportionof the liquid organic mutual solvent is selected from the C to Calcohols.

4. A method according to claim 1, wherein at least the major proportionof the liquid organic mutual solvent is isopropanol.

5. A method according to claim 1, wherein the ethylenically unsaturatedmonomer material with which the single phase is formed is selected fromthose of the designated monomers which contain not more than 14 carbonatoms.

6. A method according to claim 5, wherein the ethylenically unsaturatedmonomer material with which the single phase is formed consistsessentially of monomer selected from the class consisting of thevinylidene monomers and conjugated diene monomers.

7. A method according to claim 6, wherein the ethylenically unsaturatedmonomer material with which the single phase is formed consists at least2 percent of conjugated diene monomer.

8. A method according to claim 6, wherein the ethylenically unsaturatedmonomer material with which the single phase is formed consists at least2 percent of vinylidene monomer.

9. A method according to claim 6, wherein the ethylenically unsaturatedmonomer material with which the single phase is formed consists at least98 percent of conjugated diene monomer.

10. A method according to claim 6 wherein the ethylinically unsaturatedmonomer materials with which the single phase is formed consists atleast 98 percent of vinylidene monomer.

11. A process for forming unsaturated polymer material having a numberaverage molecular weight in the range of from 500 to 10,000 andsubstantially free from polymer material of higher molecular weightrange, said polymer material consisting essentially of conjugated dienepolymer having substituent groups as hereinafter designated, whichprocess comprises A. forming a single phase polymerization systemconsisting essentially of a combination of l. ethylenically unsaturatedmonomer material having, and polymerizable with the aid of hydrogenperoxide through, at least one group and containing not more than 14carbon atoms;

2. hydrogen peroxide, and

3. a sufi'icient quantity of liquid organic mutual solventdiluent toproduce a homogeneous solution of l (2) and (3) said quantity comprisingat least 5 ml of mutual solvent-diluent per grams of said monomermateriin which combination 4. said ethylenically unsaturated monomermaterial consists essentially of conjugated diene;

5. the ratio of said hydrogen peroxide to said ethylenically unsaturatedmonomer material lies in the range of about 0.5 to about 10 parts per100 parts of monomer, by weight; and

6. said liquid organic mutual solvent-diluent comprises at least a majorproportion of lower aliphatic saturated oxygenated solvent; and

B. heating said combination, essentially in the absence of oxygen ormaterial which appreciably decomposes hydrogen peroxide to form oxygen,at a sufficient temperature in the range of above 100 C. to about 200 C.for a sufiicient time to initiate and maintain polymerization to form,from said combination, polymer material containing substituent groupsincluding hydroxyl groups derived from the solution of the said hydrogenperoxide in the said liquid organic mutual solvent, which polymermaterial has a number average molecular weight in the aforesaid range,and has its polymerized diene units predominantly of 1,4-configuration.

12. A process for forming unsaturated polymer material having a numberaverage molecular weight in the range of from 500 to 10,000 andsubstantially free from polymer material of higher molecular weightrange, said polymer material consisting essentially of butadiene polymerhaving substituent groups as hereinafter designated, which processcomprises Aqforming a single phase polymerization system consistingessentially of a combination of l. ethylenically unsaturated monomermaterial having, and polymerizable with the aid of hydrogen peroxidethrough, at least one group and containing not more than 14 carbonatoms;

2. hydrogen peroxide, and

3. a sufficient quantity of liquid organic mutual solventdiluent toproduce a homogeneous solution of l (2) and (3) said quantity comprisingat least 5 ml of mutual solvent-diluent per 100 grams of said monomermateriin which combination 4. said ethylenically unsaturated monomermaterial consists essentially of butadiene-1,3;

5. the ratio of said hydrogen peroxide to said ethylenically unsaturatedmonomer material lies in the range of about 0.5 to about 10 parts per100 parts of monomer, by weight; and

6. said liquid organic mutual solvent-diluent comprises at least a majorproportion of lower aliphatic saturated oxygenated solvent; and

B. heating said combination, essentially in the absence of materialwhich appreciably decomposes hydrogen peroxide to formoxygen, at asufiicient temperature in the range of above 100 C. to about 200 C. fora sufficient time to initiate and maintain polymerization to form, fromsaid combination, polymer material containing substituent groupsincluding hydroxyl groups derived from the solution of the said hydrogenperoxide in thesaid liquid organic mutual solvent, which polymermaterial has a number average molecular weight in the aforesaid range,and has its polymerized diene units predominantly of l,4-configuration.

13. A method for forming a polymer material having terminal hydroxylgroups and a number average molecular weight of not over 10,000, whichmethod comprises forming a single phase polymerization system of acombination of from 2-100 percent by weight of polymerizableethylenically unsaturated monomer material having at least onesubstituent'other than hydrogen and a water solubility at 20 C. of nomore than 3.5 weight percent and from -98 percent by weight ofethylenically unsaturated monomer material having a water solubility at20 C. greater than 3.5 weight percent, said ethylenically unsaturatedmonomer materials being other than conjugated diene monomers, other thandrying oils and other than drying oil substances,

2. between 05-10 parts by weight of hydrogen peroxide per 100 parts ofmonomer,

. a liquid organic solvent for all the monomer material present and saidperoxide and any water present, said organic solvent having at least onegroup selected from the class consisting of carbinol and keto groups, I

said system being maintained free of components that decompose hydrogenperoxide at less than 100 C., and

heating said system to temperatures in the range of from above 100 C. toabout 200 C. to effect polymerization.

14. A method according to claim 13, wherein themonomer material consistessentially of vinylidene monomer.

15. A method according to claim 13, wherein said liquid organic mutualsolvent comprises an alkanol.

16. A method according to claim 13, wherein said liquid organic mutualsolvent comprises an alkanol containing not over four carbon atoms.

17. A method according to claim 13, wherein said liquid organic mutualsolvent comprises isopropanol.

18. A method for forming a polymer material having terminal hydroxylgroups and a number average molecular weight of not over 10,000, whichmethod comprises A. forming a single phase polymerization systemconsisting essentially of a combination of 1. from 2 to 100 percent byweight of polymerizable ethylenically unsaturated monomer materialhaving at least one substituent other than hydrogen and a watersolubility at 20 C. of no more than 3.5 weight percent and from 0 to 98percent by weight of ethylenically unsaturated monomer material having awater solubility at 20 C. greater than 3.5 weight percent, saidethylenically unsaturated monomer materials consisting essentially ofother than conjugated diene monomers, other than drying oils and otherthan drying oil substances, between 05-10 parts by weight of hydrogenperoxide per part of monomer,

. a liquid organic solvent for all the monomer material present and saidperoxide and any water present, said organic solvent having at least onegroup selected from the class consisting of carbinol and keto groups,

said system being maintained essentially free of components which, ifpresent, would initiate polymerization in the system at less than 100C., and

B. heating said system to sufficiently high temperatures in the range offrom above 100 C. to about 200 C. to effect polymerization.

19. A method as claimed in claim 7, wherein said ethylenicallyunsaturated monomer material further comprises acrylonitrile, and thepolymer material formed is an unsaturated butadiene-acrylonitrileinterpolymer having said terminal groups.

20. A method as claimed in claim 7, wherein said ethylenicallyunsaturated monomer material further comprises sytrene, and the polymermaterial formed is an unsaturated butadiene-styrene interpolymer havingsaid terminal groups.

2. A method according to claim 1, wherein at least the major proportionof the liquid organic mutual solvent is selected from those of saidclass of solvents which contain alcoholic hydroxyl groups.
 2. hydrogenperoxide, and
 2. hydrogen peroxide, and
 2. between 0.5-10 parts byweight of hydrogen peroxide per 100 parts of monomer,
 2. between 0.5-10parts by weight of hydrogen peroxide per part of monomer,
 2. between0.5-10 parts by weight of hyDrogen peroxide per 100 parts of monomer, 3.a liquid organic mutual solvent-diluent for all the monomer materialpresent and said hydrogen peroxide and any water present, said liquidorganic mutual solvent diluent comprising at least a major proportion oflower aliphatic saturated oxygenated solvent selected from the classconsisting of the water miscible alcohols, ether-alcohols, keto-alcoholsand ketones, said system being essentially free of oxygen and ofcomponents that decompose hydrogen peroxide to form oxygen at less than100* C., and B. heating said system at sufficient temperatures in therange of from above 100* C. to about 200* C. for a sufficient time toinitiate and effect polymerization.
 3. a liquid organic solvent for allthe monomer material present and said peroxide and any water present,said organic solvent having at least one group selected from the classconsisting of carbinol and keto groups, said system being maintainedessentially free of components which, if present, would initiatepolymerization in the system at less than 100* C., and B. heating saidsystem to sufficiently high temperatures in the range of from above 100*C. to about 200* C. to effect polymerization.
 3. a liquid organicsolvent for all the monomer material present and said peroxide and anywater present, said organic solvent having at least one group selectedfrom the class consisting of carbinol and keto groups, said system beingmaintained free of components that decompose hydrogen peroxide at lessthan 100* C., and heating said system to temperatures in the range offrom above 100* C. to about 200* C. to effect polymerization.
 3. asufficient quantity of liquid organic mutual solvent-diluent to producea homogeneous solution of (1), (2) and (3) said quantity comprising atleast 5 ml of mutual solvent-diluent per 100 grams of said monomermaterial; in which combination
 3. a sufficient quantity of liquidorganic mutual solvent-diluent to produce a homogeneous solution of (1),(2) and (3) said quantity comprising at least 5 ml of mutualsolvent-diluent per 100 grams of said monomer material; in whichcombination
 3. A method according to claim 1, wherein at least the majorproportion of the liquid organic mutual solvent is selected from the C1to C4 alcohols.
 4. A method according to claim 1, wherein at least themajor proportion of the liquid organic mutual solvent is isopropanol. 4.said ethylenically unsaturated monomer material consists essentially ofconjugated diene;
 4. said ethylenically unsaturated monomer materialconsists essentially of butadiene-1,3;
 5. the ratio of said hydrogenperoxide to said ethylenically unsaturated monomer material lies in therange of about 0.5 to about 10 parts per 100 parts of monomer, byweight; and
 5. the ratio of said hydrogen peroxide to said ethylenicallyunsaturated monomer material lies in the range of about 0.5 to about 10parts per 100 parts of monomer, by weight; and
 5. A method according toclaim 1, wherein the ethylenically unsaturated monomer material withwhich the single phase is formed is selected from those of thedesignated monomers which contain not more than 14 carbon atoms.
 6. Amethod according to claim 5, wherein the ethylenically unsaturatedmonomer material with which the single phase is formed consistsessentially of monomer selected from the class consisting of thevinylidene monomers and conjugated diene monomers.
 6. said liquidorganic mutual solvent-diluent comprises at least a major proportion oflower aliphatic saturated oxygenated solvent; and B. heating saidcombination, essentialLy in the absence of oxygen or material whichappreciably decomposes hydrogen peroxide to form oxygen, at a sufficienttemperature in the range of above 100* C. to about 200* C. for asufficient time to initiate and maintain polymerization to form, fromsaid combination, polymer material containing substituent groupsincluding hydroxyl groups derived from the solution of the said hydrogenperoxide in the said liquid organic mutual solvent, which polymermaterial has a number average molecular weight in the aforesaid range,and has its polymerized diene units predominantly of 1,4-configuration.6. said liquid organic mutual solvent-diluent comprises at least a majorproportion of lower aliphatic saturated oxygenated solvent; and B.heating said combination, essentially in the absence of material whichappreciably decomposes hydrogen peroxide to form oxygen, at a sufficienttemperature in the range of above 100* C. to about 200* C. for asufficient time to initiate and maintain polymerization to form, fromsaid combination, polymer material containing substituent groupsincluding hydroxyl groups derived from the solution of the said hydrogenperoxide in the said liquid organic mutual solvent, which polymermaterial has a number average molecular weight in the aforesaid range,and has its polymerized diene units predominantly of 1, 4-configuration.7. A method according to claim 6, wherein the ethylenically unsaturatedmonomer material with which the single phase is formed consists at least2 percent of conjugated diene monomer.
 8. A method according to claim 6,wherein the ethylenically unsaturated monomer material with which thesingle phase is formed consists at least 2 percent of vinylidenemonomer.
 9. A method according to claim 6, wherein the ethylenicallyunsaturated monomer material with which the single phase is formedconsists at least 98 percent of conjugated diene monomer.
 10. A methodaccording to claim 6 wherein the ethylinically unsaturated monomermaterials with which the single phase is formed consists at least 98percent of vinylidene monomer.
 11. A process for forming unsaturatedpolymer material having a number average molecular weight in the rangeof from 500 to 10, 000 and substantially free from polymer material ofhigher molecular weight range, said polymer material consistingessentially of conjugated diene polymer having substituent groups ashereinafter designated, which process comprises A. forming a singlephase polymerization system consisting essentially of a combination of12. A process for forming unsaturated polymer material having a numberaverage molecular weight in the range of from 500 to 10, 000 andsubstantially free from polymer material of higher molecular weightrange, said polymer material consisting essentially of butadiene polymerhaving substituent groups as hereinafter designated, which processcomprises A. forming a single phase polymerization system consistingessentially of a combination of
 13. A method for forming a polymermaterial having terminal hydroxyl groups and a number average molecularweight of not over 10,000, which method comprises forming a single phasepolymerization system of a combination of
 14. A method according toclaim 13, wherein the monomer material consist essentially of vinylidenemonomer.
 15. A method according to claim 13, wherein said liquid organicmutual solvent comprises an alkanol.
 16. A method according to claim 13,wherein said liquid organic mutual solvent comprises an alkanolcontaining not over four carbon atoms.
 17. A method according to claim13, wherein said liquid organic mutual solvent comprises isopropanol.18. A method for forming a polymer material having terminal hydroxylgroups and a number average molecular weight of not over 10,000, whichmethod comprises A. forming a single phase polymerization systemconsisting essentially of a combination of
 19. A method as claimed inclaim 7, wherein said ethylenically unsaturated monomer material furthercomprises acrylonitrile, and the polymer material formed is anunsaturated butadiene-acrylonitrile interpolymer having said terminalgroups.
 20. A method as claimed in claim 7, wherein said ethylenicallyunsaturated monomer material further comprises sytrene, and the polymermaterial formed is an unsaturated butadiene-styrene interpolymer havingsaid terminal groups.